Laser ablation and filtration apparatus and process for removal of hydrocarbons and contaminants

ABSTRACT

A laser ablation and filtration process and apparatus wherein liquid containing hydrocarbons or other contaminates is purified. The liquid is exposed to laser energy at one or more selected wavelengths wherein the laser energy travels through the liquid and reaches the hydrocarbons or other contaminates and vaporizes, denatures, breaks down, neutralizes, renders inert and/or separates the hydrocarbons or contaminates from the liquid. A laser source is positioned in or on a vessel based on pre-set parameters to maximize exposure of the liquid to the laser energy, including sizing parameters, angle and inclination of the laser, retention time for the laser process to be applied and geometry of the containment for proper inclination. One or more collection chambers, which may include perforated membranes may be included to collect gases, separated hydrocarbons or contaminates and other by-products of the process. The vessel utilized may be submergible in water to pull or flow contaminated water therethough. The vessel may also be utilized outside a body of water wherein contaminated water from a source is introduced within the vessel.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of and/or priority to U.S.Provisional Patent Application Ser. No. 62/255,156, filed on 13 Nov.2015, which is hereby incorporated herein by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable

REFERENCE TO A “MICROFICHE APPENDIX”

Not applicable

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a laser ablation and filtration processand apparatus, wherein laser ablation and filtration is utilized toremove hydrocarbons, including oil, natural gas, grease and/or othercontaminants, including pathogens, bacteria, and/or other unwantedorganisms, from a liquid or fluid, e.g., fresh or salt water.

2. General Background of the Invention

Removing hydrocarbons and contaminants from water is a continuousworldwide challenge in many industries, including in the oil and naturalgas industry. Conventional prior art methods require the use ofchemicals and filtration media, which become exhausted and need to becontinuously disposed of and replaced. The disposal of filtrationmaterials generates additional waste and expense. Water filtration toremove contaminants such as hydrocarbons has a direct impact on oil andgas industries, the shipping industry, naval operations, and many otherindustries, entities, and organizations.

For example, several common standards per government regulation(including, for example, International Maritime Organizationrequirements MEPC.107(49)), for water from various processes is that itmust have less than 15 ppm of hydrocarbons (15 microliter/liter), beforedilution, before it can be discharged or disposed of back into theocean. There are also regulations for reinjection of fluid down hole,which include the Federal Safe Water Act and UIC Regulations.

There is thus a need in the art for a method for removal of hydrocarbonsthat reduces or eliminates the use of chemicals and/or filtration mediawhen removing hydrocarbons and other contaminates from water or otherliquids.

There is also a need in the art to reduce or eliminate the amount ofchemical and filtration waste associated with conventional prior artmethods for removing hydrocarbons from a liquid, wherein chemicalsand/or filtration media become exhausted and continually need to bedisposed of and replaced.

There is also a need in the art to reduce the amount of expenseassociated with replenishing chemicals and filtration media anddisposing of the chemicals and filtration media via conventional priorart methods for removing hydrocarbons from a liquid, wherein chemicalsand/or filtration media become exhausted and continually need to bedisposed of and replaced.

BRIEF SUMMARY OF THE INVENTION

The apparatus(es) and process(es) of the present invention solves theproblems confronted in the art in a simple and straightforward manner.In various embodiments, a laser ablation and filtration apparatus andprocess of the present invention offers a more environmentally safe andeffective alternative to purifying water containing hydrocarbons orother contaminates because it uses laser light energy, which does notrequire the use of consumable materials such as chemicals.

Various embodiments of the laser filtration method and apparatus of thepresent invention can be used to assist filtration methods that utilizechemicals and filtration media to remove hydrocarbons and othercontaminates from water, wherein less chemicals and filtration mediawill be used.

Various embodiments of the laser filtration method and apparatus of thepresent invention can be used to replace conventional prior artfiltration methods that utilize chemicals and filtration media to removehydrocarbons and other contaminates from water wherein no chemicals orfiltration media are needed for use with the process.

Generally, laser light is an intense, collimated and/or focused beam ofvisible or invisible light radiation. When exposed to laser light,hydrocarbons, including grease, natural gas and oil, and othercontaminants, including pathogens or bacteria or other organisms absorbthe laser light energy. The laser light energy can denature, vaporize,break down, alter, kill, or otherwise render inert the hydrocarbon orcontaminate, respectively.

Different hydrocarbons and contaminates have different laser energyabsorption and fluorescence characteristics. The laser energy absorptionand fluorescence characteristics of a hydrocarbon or contaminate mayalso vary depending on the concentration of the hydrocarbon orcontaminate. Laser light at one wavelength may be more effective on onetype of hydrocarbon or contaminate present in a liquid, while laserlight at a different wavelength may be more effective on a second typeof hydrocarbon or contaminate present in the liquid.

In various embodiments the laser ablation and filtration process of thepresent invention comprises:

Obtaining samples of contaminated liquid that will undergo the laserablation and filtration process;

Gathering data on absorption and fluorescence characteristics of theliquid and of the hydrocarbons present in the liquid, e.g., absorptionand fluorescence characteristics that help identify the liquid and theparticular type(s) of hydrocarbon or contaminants in the liquid, whereinabsorption characteristics help inform the decision on which laser lightwavelengths will be effective in the laser ablation and filtrationprocess, e.g., the ability of the laser light to travel through theliquid to the targeted hydrocarbon or contaminate, to be absorbed by theliquid and to be absorbed by the targeted hydrocarbon or othercontaminate;

Selecting a specific wavelength of pulsed, modulated, or continuous wavelaser energy at a sufficient energy density to target one or moreunwanted hydrocarbons or other contaminants;

Flowing the contaminated water into a containment vessel comprising adesired laser scanner configuration;

Applying laser energy throughout the contaminated liquid, within thecontainment vessel at the selected wavelength and frequency;

Preferably applying laser energy for a selected time interval and at aselected temperature;

Wherein the hydrocarbon, gas, grease and/or other targeted contaminatesare vaporized, denatured, rendered inert and/or separated from theliquid, e.g., rises to the top of the liquid, where they can beseparated, and flowed to a collection reservoir;

Gathering data on the amount of hydrocarbon or other contaminantremaining in the liquid after performing the above-steps;

Repeating the above-steps if necessary until only a desired amount ofthe hydrocarbon or other contaminants remains in the liquid, e.g. under15 ppm (15 microliter/liter); and/or

Repeating the above-steps with one or more different wavelengths totarget one or more different hydrocarbons or contaminates that arepresent in the liquid.

In various embodiments the laser ablation and filtration process of thepresent invention comprises obtaining samples of contaminated liquidthat will undergo the laser ablation and filtration process.

Data on absorption and fluorescence characteristics of the liquid and ofthe hydrocarbons present in the liquid is obtained, e.g., throughrunning tests on the contaminated liquid. Absorption and fluorescencecharacteristics help identify the liquid and the particular type(s) ofhydrocarbon or contaminants in the liquid. Absorption characteristicsalso help inform the decision on which laser light wavelengths will beeffective in the laser ablation and filtration process, e.g., theability of the laser light to travel through the liquid to the targetedhydrocarbon or contaminate, to be absorbed by the liquid and to beabsorbed by the targeted hydrocarbon or other contaminate.

Selecting a specific wavelength of pulsed, modulated, or continuous wavelaser energy at a sufficient energy density to target one or moreunwanted hydrocarbons or other contaminant.

A sufficient energy density can be 0.5 J/cm2, for example, if targetinghydrocarbons, or 1.5 J/cm2, if targeting a pathogen.

The contaminated water can then be flowed, pulled, sucked, or otherwisedrawn into a containment vessel or pipe comprising a desired laserscanner configuration.

Laser energy is applied throughout the contaminated liquid, within thecontainment vessel at the selected wavelength.

Preferably laser energy is applied for a selected time interval and at aselected temperature.

The selected time interval preferably is chosen to maximize absorption,vaporization, denaturalization, or the rendering inert of thecontaminants in the water. The desired time interval can be optimized bytesting and adjusting based on data obtained from one or more processedsamples of the liquid after undergoing a laser ablation process. Thelonger the contaminated water is exposed to the laser energy, thecleaner the water will become.

For example, if laser energy is applied to a closed container or vessel,laser energy may be applied for 1 to 5 minutes. After the 1 to 5minutes, the water should be visibly clearer. Also, produced gas, e.g.,bubbles rising in the liquid, or other evidence of a contaminate havingbeen separated from the liquid, can be present as visible indictors thatthe laser ablation process was effective to clean or purify the water.The selected time interval can be extended as necessary to achievecleaner or maximum desired results. Optionally, the process can berepeated for 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 minuteintervals, or longer as desired, for example. Testing of samples of theprocessed water can be performed after running each, or after one ormore selected, laser ablation processes to determine if a desired resulthas been achieved, e.g., if the processed liquid will pass regulationsfor purification that will allow the water to be returned to the source.

If contaminated water is flowed through a vessel or pipe for example,the length of time the laser energy is applied will be based on thelength of time it takes for the liquid to flow through the vessel orpipe with exposure to the laser path. In this embodiment, using mirrorsto bounce the laser energy around the vessel or pipe, or adjusting theconfiguration of the laser beam, e.g., so that it is a cone or tubeconfiguration, can be desirable to maximize exposure of the liquid tothe laser energy while the contaminated liquid is traveling through thevessel or pipe, for example.

The selected temperature can be room temperature. The temperature of theliquid is not as important as other parameters and can vary and still beeffective at a wide range of temperatures.

Preferably during the laser ablation process, the hydrocarbon, gas,grease and/or other targeted contaminates are vaporized, denatured,rendered inert and/or separated from the liquid, e.g., rises to the topof the liquid to be separated and flow to a collection reservoir.

Data preferably is gathered on the amount of hydrocarbon remaining inthe liquid after performing the above-steps.

The above-steps can be repeated if necessary until only a desired amountof the hydrocarbon remains in the liquid, e.g. under 15 ppm (15microliter/liter).

The laser ablation process can also be repeated with one or moredifferent wavelengths to target one or more different hydrocarbons orcontaminates that are present in the liquid.

In various embodiments, after purifying the liquid, the liquid may beflowed to a reservoir, the ocean, downhole, or otherwise returned to asource for the water.

In various embodiments, a specific wavelength of pulsed, modulated, orcontinuous wave laser energy at a sufficient energy density is used totarget unwanted contaminants, such as hydrocarbons from crude oil, inwater, or other liquids, and used to decrease and/or completely removetheir concentration from the liquid.

Pulse duration of a wavelength can be at 10 nanoseconds, or 100nanoseconds, for example, or it can be Continuous Wave (CW) or modulatedwave. Preferably the pulse duration and type of pulse parameter isselected so that the laser energy reaches an effective energy density oflight that causes the reaction with the contaminate in the liquid. Asindicated pulse duration can be set at 10 or 100 nanoseconds. Acontinuous wave or CW is a continuous laser beam without pulses that isvery intense. A modulated CW wave is also a continuous laser beam withhigh and low peaks of energy.

An energy density will be sufficient if it facilitates the desiredreaction or process to denature the targeted contaminants. A desiredenergy density can be determined by testing one or more samples ofprocessed liquid, after it has undergone a laser ablation process, andthen adjusting the energy density to help achieve more effectiveresults. The process can be repeated for a particular liquid to undergothe ablation process, until optimal parameters are identified for theparticular contaminated liquid.

The above-described testing process can also be conducted to determineother optimal parameters for the laser ablation process for a particularcontaminated liquid.

Various embodiments of the apparatus and process of the presentinvention will use absorption characteristics and/or fluorescence of thecontaminant material, and will use tuned high power lasers to vaporize,denature, and/or separate the contaminants from water. Examples of highpower lasers include laser sources, such as pulsed, continuous wave, ormodulated continuous wave lasers that typically emit ten watts or moreof average power, up to multiple kilowatts or megawatts.

For example, 70 W and 100 W units have been tested and more powerfullaser sources foreseeably will increase efficacy of the process.Repeated testing with high frequency 1064 nm laser pulses, e.g., 200,000to 1,000,000 pulses per second, has established that hydrocarbon levelsin water are successfully reduced every time. Preliminary testing withlow frequency 532 nm laser pulses, e.g., 10 pulses per second, haseffectually produced clearer water, visually, and appears tosuccessfully vaporize hydrocarbon contaminants. It is foreseen thattesting with high frequency, e.g., 200,000 to 1,000,000 million pulsesper second, of 532 nm laser sources will provide even better productionrates and measurements. It is foreseen that testing with low or highfrequency, e.g., 10 to 1,000,000 million pulses per second, of 532 nmlaser energy will effectively process and clean contaminated liquid.

In various embodiments tuning parameters may include, but are notlimited to, wavelength, fluence, pulse duration, modulation rate, pulseprofile, beam diameter, pulse frequency, energy, and/or focal distance.

In various embodiments the laser light energy can be fired directly intothe liquid from a source or with the assistance of a delivery systemsuch as mirrors, fiber optics, articulated arms, and laser scanners. Thenecessary energy density or fluence of the laser that is needed tofacilitate the reaction can be achieved by firing the laser directlyfrom a source or by using optics such as collimators, mirrors, prisms,custom optics, and focusing lenses to achieve desired parameters.

In various embodiments, the laser energy is absorbed by the contaminantand can convert a part or all of the contaminant from a liquid stateinto a gaseous state, allowing it to float to the surface and separatefrom the liquid. The laser energy can also disrupt bonds and/or denatureor decompose the contaminant. For example, molecular bonds can bebroken, resulting in both chemical and/or physical changes of thematerial. This process may render hazardous materials to chemicallyand/or physically change to be inert. Laser pulses result inphotomechanical, photochemical, and photothermal processes that act uponand affect the hydrocarbon and/or other contaminant.

In various embodiments, the path and intensity of the laser may beabsorbed into the liquid over a long distance of travel and/or terminateat a target or surface. A target can be simply an inert energy dumpmaterial or can be made of a material that will facilitate plasmaformation and cavitation bubbles. An inert energy dump material may beselected based on the wavelengths to be utilized in the laser ablationapparatus and/or process wherein the energy dump will sufficientlyabsorb the laser energy and terminate or end the laser path. An energydump can be made of a material such as metal or ceramic that isappropriate for the wavelength or wavelengths being used. A metalcommonly used in energy dumps is aluminum. Titanium is an example ofanother metal that may be used as an energy dump. Other suitable metalsmay also be utilized based on capability to absorb the wavelengths to beused.

A target could also be an energy dump that is a chamber containing aliquid or fluid or other material that strongly, or will sufficiently,absorb the laser wavelength or wavelengths used in the process orapparatus.

Ceramic, titanium and aluminum are examples of materials that may beused as an energy dump and which facilitate formation of cavitationbubbles, e.g., for use with 1064 nm, 532 nm, 355 nm, and/or 266 nmwavelengths. Other examples of inert energy dumps include graphite andglass, e.g., for use with 1064 nm, 532 nm, 355 nm, and/or 266 nmwavelengths. Bubbles can also form in the liquid itself without need ofhitting a solid surface.

The laser energy can also be used to create bubbles and micro-bubbles orcavitation bubbles which help facilitate the separation of thecontaminant from the liquid. These cavitation bubbles can help carry thecontaminant material to the surface for flowing to a collectionreservoir. The bubbles may assist in contaminant removal by facilitatingthe formation of a hydrophobic and/or hydrophilic film around eachbubble that is carried up to the surface. The contaminant may alsodevelop an electrostatic or other attraction to the bubbles that areformed and/or to itself.

Laser energy can also be used to break down and denature contaminants. Aspecific wavelength is preferably selected to target a contaminant inthe water.

In various embodiments, the laser ablation process may also break downthe contaminant into small particles such as microparticles ornanoparticles.

In various embodiments, the laser ablation process may also producemicro-bubbles, which aid in separating the hydrocarbon or contaminantfrom the liquid.

A key principle with this technology is choosing a wavelength, ormultiple wavelengths, that penetrates through the liquid, such as water,and absorbs into the contaminant. If the wavelength cannot pass throughthe liquid, then it will not reach the contaminant. In variousembodiments, a wavelength with some absorption into the liquid may bedesirable as it will still reach the contaminant, will weaken anddissipate after a certain distance, and will cause additional reactionssuch as heating up the liquid, which may be beneficial to the process invarious embodiments. Heating the liquid with the laser or with othermethods is foreseen to be beneficial as there is an inverse relationshipbetween temperature and the solubility of gas in water. A highertemperature of the liquid foreseeably will help the reaction go faster.

In various embodiments, one or more wavelengths can be used individuallyor simultaneously, e.g., 532 nm and 1064 nm used simultaneously orindividually.

In various embodiments, the laser ablation process may operateefficiently on its own to purify liquid and remove unwanted hydrocarbonsand contaminants, without use of an additive or other conventionalfiltration methods.

In various embodiments, the laser ablation process is used inconjunction with additives, e.g., adding emulsifiers or surfactants,that at a Critical Micelle Concentration level help isolate and removethe contaminant from the liquid.

In various embodiments, the laser ablation process is used inconjunction with chemicals and/or filtration medium to assist inseparating or removing hydrocarbons and other contaminates from theliquid.

In various embodiments, the laser ablation process is used inconjunction with additives and other chemicals and filtration medium toassist in separating or removing hydrocarbons and other contaminatesfrom the liquid.

In various embodiments, the apparatus of the present invention comprisesa containment vessel. The containment vessel is for containing liquid tobe purified. The containment vessel may comprise a laser source, e.g. alaser scanner, for providing and directing laser light energy into andthrough the liquid to be purified. The containment vessel can containthe contaminated liquid to be purified and the laser energy during thetreatment process. In some embodiments, contaminated water can flowthrough a vessel, e.g., continuously flow through vessel, during thelaser ablation process, and exit the vessel when it reaches the end ofthe vessel as processed or purified or clean water.

The position of a laser source, e.g. a laser scanner within or outsideof a vessel, e.g., a containment vessel, is important to the laserremoval process. Preferably the laser is positioned within or outsidethe vessel so as to maximize exposure of the liquid to the laser energy.The position of the scanner affects the path of the laser energy. Toprovide this controlled containment, preferably certain sizingparameters are applied including angle and inclination of the laser,retention time for the laser process to be applied and geometry of thecontainment for proper inclination, preferably to achieve maximumexposure of the liquid to the laser energy. After evaluating thecontaminated liquid and applying selected parameters, and re-testing thewater, the parameters can be adjusted based on the type and amount ofcontaminants still present in the liquid, to help achieve maximumexposure and effective removal of contaminants for the laser ablationprocess.

Additionally certain mechanical devices may be included to assist inremoval of the oil, grease, gas or other contaminate and for removal ofbyproduct created by the laser, i.e. residual oil.

Preferably compartmental containment is provided as a vital feature forseparation and removal.

In addition to residual oil, micro-bubbles may be produced as abyproduct of the laser process. Due to their size and physicalcharacteristics, sub 50 micron by definition, the containment andcompartmentalization process becomes more important and crucial to themanagement of the process. Compartmentalization and sizing of thecompartments based on flow and flow characteristics will add to thesuccess of the overall process of laser ablation and micro-bubbles.

In addition to the laser ablation process and any micro bubbles that maybe formed, additional micro bubbles can be added to the system to betterfacilitate filtration and separation of materials. These bubbles can becreated by mechanical means, which include mechanical agitation,eductor, and dissolved air pump.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

For a further understanding of the nature, objects, and advantages ofthe present invention, reference should be had to the following detaileddescription, read in conjunction with the following drawings, whereinlike reference numerals denote like elements and wherein:

FIGS. 1-1A illustrate an example of absorption and fluorescence spectradata of hydrocarbons in contaminated water, as obtained in an embodimentof the process of the present invention;

FIGS. 2-2A illustrate a prior art graph depicting absorption spectra ofoil;

FIGS. 3-3A illustrate a prior art graph depicting absorption spectrum ofliquid water across a wide wavelength range;

FIGS. 4-4A illustrate a view of contaminated water (on the left) and thesame water after applying a laser ablation and filtration process of thepresent invention (on the right) and the absorption spectra of thecontaminated and cleaned water;

FIG. 5 illustrates a laser scanner positioned near a corner junction ofpipes, firing parallel to the flow direction in an embodiment of themethod of the present invention;

FIG. 6 illustrates a top view of a laser scanner above a pipe, firingperpendicular to the flow direction;

FIGS. 6A-6C illustrate side views of a laser scanner above a pipe,firing perpendicular to the flow direction;

FIGS. 7A-7E illustrates examples of laser source or scannerconfigurations in various embodiments of the method of the presentinvention;

FIGS. 8A-8D illustrate examples of how one or more laser scans can bebounced around inside a vessel, chamber, tube or pipe for maximumexposure in various embodiments of the method of the present invention;

FIG. 9 illustrates a laser path in a vessel, chamber, tube, or pipehaving liquid therein wherein the laser light “wall” bounces around inthe vessel, chamber, tube, or pipe increasing the amount of exposure ofthe liquid to the laser as the liquid flows therethrough in anembodiment of the method and apparatus of the present invention;

FIG. 10 is a schematic diagram of an embodiment of the process of thepresent invention wherein contaminated liquid flows into a container toundergo a laser ablation process, wherein separated or transformedhydrocarbons are separated from the contaminated liquid and flowed to acollection chamber, and wherein clean water exits the container or pipe;

FIGS. 11-12 are images of bubbles formed in water during a laserablation process; and

FIG. 13 is an image of contaminated water with a red aiming beam used inthe dark to show the path that the laser energy would follow.

DETAILED DESCRIPTION OF THE INVENTION

The apparatus and process of the present invention offers a moreenvironmentally safe and effective alternative to purifying watercontaining hydrocarbons because it uses laser light energy, which doesnot require the use of consumable materials such as chemicals.Embodiments of the laser ablation and filtration method and apparatus ofthe present invention can be used to assist and/or replace currentfiltration methods.

Before turning to FIGS. 1 and 4-13, which illustrate examples of variousembodiments of the method and apparatus of the present invention,reference is made to FIGS. 2-3.

FIGS. 2-2A illustrate a chart showing absorption spectra of oil, fromOpen Journal of Marine Science: Detecting Oil Spill Contamination UsingAirborne Hyperspectral Data in the River Nile, Egypt (available at:http://file.scirp.org/Html/htmlimages/9-1470129x/297a010a-dc5f-4305-adf9-a7cd43031658.png), which is hereby incorporated herein by reference. Asdiscussed in detecting Oil Spill Contamination Using AirborneHyperspectral Data in the River Nile, Egypt, the interaction between theoil slick and the optical electromagnetic radiation is governed by thelight transmission and reflection through the oil slick. Fourrecognizable windows of absorption of electromagnetic radiation with oilcontamination, are 1) visible range from 400-800 μm; 2) near infraredrange from 1100 μm to 1220 μm; 3) near infrared range from 1600 μm to1760 μm; and 4) short wave infrared range from 2200 μm to 2350 μm[12]-[14]. FIG. 2 shows the spectral response of the in-situ samplingsites in the Nile River in correlation with the predefined fourabsorption windows.

FIGS. 3-3A illustrate a chart showing absorption spectrum of liquidwater across a wide wavelength range. Strong Bands: 2900 nm, 1950 nm,1450 nm. Medium bands: 1200 nm, 900 nm. Weak bands: 820 nm, 730 nm. Thehydroxide (OH) bonds of water, for example have a strong absorption near3,000 nm or 3 microns. (The chart shown is available at:http://omlc.org/spectra/water/abs/index.html (which is herebyincorporated herein by reference)).

Turning now to FIGS. 4-13, the laser ablation apparatus 10 of thepresent invention comprises a vessel 11 (see FIGS. 5-6, 8-9). A vessel11, which may be a containment vessel or other container or a pipe ortube, contains or houses a liquid 20 to be processed and/or purifiedduring the laser ablation and filtration process, wherein thecontaminated liquid 20 may be flowed therethrough, or contained within avessel 11 while undergoing laser ablation. The laser ablation apparatus10 has a laser source or scanner 40 for providing and directing laserlight energy 12 to the liquid 20 to be purified. In various embodiments,the vessel 11 contains the contaminated liquid 20 that will undergo theablation and filtration process and the laser energy 12 during thetreatment process. The process may utilize a wide range of wavelengthsfrom the electromagnetic spectrum such as, but not limited to UV light,wavelengths from the visible color spectrum such as green and bluelasers, infrared lasers, as well as others. For example, 1064 nm, 532nm, 355 nm, and/or 266 nm lasers can be used individually orsimultaneously for optimal effects. For example, 1064 nm, 532 nm, 355nm, and/or 266 nm laser radiation can be obtained from a Nd:YAG laser.

The laser 40 may be positioned within or outside a vessel 11. A vessel11 may be a containment vessel or container manufactured for the laserablation and filtration process. A vessel 11 may also be an existing orprior art vessel or container adapted for use with the laser filtrationprocess. Alternatively, the vessel 11 may be a pipe or tube in thefield, for example, and the process may be applied within a pipe or tubein the field. The process may be applied directly to a vessel/pipe/tube11 in the field via inserting a laser source 40 into thevessel/pipe/tube 11 or adding a laser source 40 attachment to thevessel/pipe/tube pipe 11.

If a laser 40 is positioned outside a vessel 11, a window 90 preferablyis provided on the vessel 11, which will allow the laser energy 12 totravel through the window 90 and within the vessel 11 to the liquid 20housed within (see FIG. 8).

The position of a laser source 40 within or outside a vessel 11 isimportant to the laser removal process. Preferably the laser 40 ispositioned so as to maximize exposure of the liquid 20 and contaminatesto be removed by the laser energy. The position of the scanner affectsthe path 15 of the laser energy 12. To provide a desired controlledcontainment and laser ablation and filtration process, certain sizingparameters are preferably applied including angle and inclination of thelaser source 40, retention time for the laser process to be applied andbased on geometry of the containment or vessel 11 for properinclination.

In various embodiments one or more mirrors 80 may be utilized to affectthe path 15 of the laser energy 12 wherein laser energy 12 will bounceoff the one or more mirrors 80.

Additionally certain mechanical devices can be included for removal ofoil, grease, gas or other contaminates and for removal of one or moreby-products created by the laser process, i.e. residual oil ormicrobubbles.

Preferably compartmental containment is provided as a vital feature forseparation and removal of unwanted contaminates. In addition to residualoil, micro-bubbles may be produced as a byproduct of the laser process.Due to their size and physical characteristics, sub 50 micron bydefinition, the containment and compartmentalization process becomesmore important and crucial to the management of the process.Compartmentalization and sizing of the compartments based on flow andflow characteristics will add to the success of the overall process oflaser ablation and micro-bubbles.

A vessel or container 11 may comprise a collection chamber, or a seriesof chambers. In various embodiments, the chambers may have perforatedmembranes, which allow clean water to pass therethrough but capturesseparated contaminates.

In various embodiments a ventilation system may be integrated to collectand separate gasses that are created in the ablation process. Preferablya gas collection area or mechanism will be physically, and/or opticallyseparated from the path 15 of the laser beam 12 in order to avoid anyrisk of potentially igniting flammable gasses or materials.

Turning now to the laser ablation process, in various embodiments thelaser ablation process preferably comprises obtaining one or moresamples of contaminated water or liquid that will undergo the laserablation process. Absorption, fluorescence, and microscopy, of the oneor more samples are preferably evaluated. Absorption, fluorescence andmicroscopy information, characteristics and/or data can be evaluated andrecorded by using absorption spectroscopy such as ultraviolet-visiblespectroscopy. For example, a spectrometer such as a SILVER-Nova, that iscommercially available at http://www.stellarnet.us, can be used.

Absorption and fluorescence characteristics, information and data helpwith identifying the type of liquid or fluid, the type of hydrocarbon(s)within the fluid and also other types of contaminates that may bepresent. Video microscopy can help with identifying physical changes ofthe oil droplets, solid particles, and gas bubbles. The data may becollected by spectroscopic instruments, video microscopy instruments,gravimetric testing, and/or with other suitable analytical tools,currently existing or which may be developed in the future. Absorptioncharacteristics also help inform the decision on which wavelengths areselected for the laser based on the wavelength's ability to travelthrough the particular liquid, the capability of being absorbed by theliquid and capability of being absorbed by the hydrocarbon or othertargeted contaminate.

After evaluating absorption, fluorescence and microscopy characteristicsand/or other collected data for the purpose of determining the liquidcomposition and contaminants present therein, the process includesselecting a specific or desired wavelength of pulsed, modulated, orcontinuous wave laser energy at a sufficient energy density to target aparticular, or more than one, unwanted hydrocarbon or other contaminant,based on the absorption characteristics of the hydrocarbons,contaminates and the liquid.

Next, contaminated water will be flowed, pulled or otherwise into thecontainment vessel. A desired laser source and configuration will beselected. Laser energy can then be supplied throughout the contaminatedliquid, within the containment vessel, at the selected wavelength. Aselected time interval and temperature may also be utilized. The laserenergy will travel through the liquid and be absorbed by thehydrocarbon, gas, grease and/or other targeted contaminate forvaporizing, denaturing, rendering inert, killing and/or separating fromthe liquid, e.g., rising to the top of the liquid wherein it may flow toa collection reservoir or chamber. Examples of laser scannerconfigurations will be discussed further below with reference to FIGS.5-9.

In various embodiments, separated hydrocarbon, gas, grease, and/or othertargeted contaminates are disposed of after removal, e.g. flowed to acollection chamber or reservoir or sump 16.

A vessel 11 may be configured so that separated or transformedhydrocarbons or contaminates flow to the top of the liquid, wherein theseparated or transformed hydrocarbons can be separated from the liquidthrough gravity separation, for example, and then flowed to a collectionchamber or reservoir or sump 16. To remove separated contaminates,skimmer devices such as spillover weirs, rotatable paddles, or flightand rake systems, may be used to assist with removal and flow ofseparated materials to a collection chamber or collections sump 16. FIG.10 is a schematic diagram illustrating an embodiment of the method,wherein contaminated water 20 flows into vessel 11. Separated ortransformed hydrocarbons or contaminates can flow to the top of theliquid and to a collection chamber 16. Prior to flowing to a collectionchamber they could also be flowed through skimmer devices such asspillover weirs, rotatable paddles, or flight and rake systems.Processed water exits vessel 11 after the laser ablation process iscomplete.

A collection chamber or series of chambers, perforated membranes, or aventilation system preferably will be integrated to collect and separatethe gasses that are created in the ablation process. Preferably this gascollection area or mechanism is physically and/or optically separatedfrom the path of the laser beam in order to avoid any risk ofpotentially igniting flammable gasses.

Additional reference is made to U.S. Pat. Nos. 8,834,723; 8,834,724;9,095,786; and to U.S. Patent Application Publication No.US20160009571A1, each of which is hereby incorporated herein byreference, which are directed to apparatuses and methods for separationand removal of hydrocarbons or other contaminates from a liquid.

After laser energy is applied under selected parameters and for aselected time interval, data may be gathered and collected on the one ormore samples of the processed or purified liquid, including on theamount of hydrocarbon or contaminants remaining in the liquid, as wellas the type of hydrocarbon or contaminants that remain in the liquid. Ifnecessary, the process may be repeated until only a desired minimumamount of the hydrocarbon or contaminate remains in the liquid, e.g.under 15 ppm (15 microliter/liter) hydrocarbon. The same liquid may alsoundergo the laser ablation and filtration process again wherein one ormore different selected wavelengths are utilized to target one or moredifferent hydrocarbons or contaminates that may be present in theliquid.

In various embodiments, after purifying the liquid, the liquid may bereturned to a reservoir, or to the source of the liquid or useddownhole.

In various embodiments, more than one laser source or scanner, e.g. two,three, four, five or more, may be used, each laser source or scannertuned to the same parameters, to increase exposure of the liquid to thelaser beam by having multiple laser paths directed through the liquid atthe same time.

In various embodiments, more than one laser source or scanner, e.g. two,three, four, five or more, may be used, each laser source or scannertuned to one or more different parameters, e.g., one or more differentwavelengths, to send laser beams at different wavelengths and/ordifferent parameters through the liquid at the same time.

Turning now to FIG. 1, an example will be discussed. FIG. 1 illustratesabsorption and fluorescence data 13 gathered while performing the laserablation process on a sample of contaminated water. The absorption andfluorescence spectra of hydrocarbons is shown. The lines designated byA-A highlight the 500-550 nm peak.

Example

The following example is illustrative and is not exhaustive.Hydrocarbons present in a liquid are measured via an ASDspectroradiomete, to absorb around 400-800 nm, with a peak fluorescencearound 500-550 nm (see FIGS. 1-1A and FIGS. 2-2A). Laser radiation canbe used to target the entire hydrocarbon that is known to fluoresce atthese wavelengths. For example a 532 nm laser radiation is an effectivewavelength because this particular wavelength passes through both freshand salt water fairly well (FIG. 3) and is also strongly absorbed byhydrocarbons. Other wavelengths, selected based on their absorptioncharacteristics into a particular contaminant, and the fluid can also beused. For example, wavelengths may be selected that will penetrate theliquid and will be absorbed by the hydrocarbon and cause vaporization,denaturing or separation of the hydrocarbon from the fluid. Also, invarious embodiments a wavelength will be selected so the liquid absorbssome of the laser light energy while the laser light energy is passingthrough the liquid.

UV laser radiation can also be used to neutralize pathogens, bacteria,and other unwanted organisms in water.

The laser ablation and filtration apparatus and process offers a moreenvironmentally safe and effective alternative to purifying waterbecause it uses laser light energy, which does not require the use ofconsumable materials such as chemicals. Laser ablation filtrationmethods can be used to assist and/or replace prior art or currentfiltration methods.

In various embodiments, laser filtration methods can be used to assistand/or replace current filtration methods.

Experimental Study

FIGS. 4-4A illustrate before and after results for water 20 processedand/or purified with a laser ablation process. FIG. 4A is a photographview illustrating a sample of contaminated water 20, and then a sampleof processed water 30. Contaminated water 20 had hydrocarbon levelsmeasuring at 21.42 ppm. After going through a laser ablation andfiltration process the processed water 30 had hydrocarbon levelsmeasuring at 6.70 ppm. During the experimental study, 1064 nm 100 nslaser pulses in a prototype system were used to successfully reduce theconcentration of a Gulf of Mexico offshore location for a Major OilCompany oil dispersion in water, at room temperature, by 75% byvaporizing the oil that was emulsified in the water. As shown in FIG.4A, the water turned visibly clearer after exposure to the laser pulses,a gas was generated, and the measured parts per million of thehydrocarbon content decreased by 75%.

In various embodiments one or more different selected wavelengths may beused individually or at the same time to achieve optimal results whilepurifying water and to target one or more different kinds ofcontaminates at the same time.

In various embodiments a wavelength between 266 nm and 1064 nm may beutilized to purify water containing hydrocarbons. In other embodiments awide range of wavelengths from the electromagnetic spectrum can beutilized to target varying hydrocarbons or other contaminates based onthe particular wavelengths effect on the contaminants or hydrocarbons.

In various embodiments multiple different wavelengths may be utilized toprocess and/or clean water containing a plurality of different types ofhydrocarbons or other containments, the wavelengths selected based onabsorption and/or florescence and/or microscopy characteristics or dataof the liquid and particular hydrocarbons at issue so that the laserenergy will be able to travel through the liquid, reach the hydrocarbonor other contaminate, and vaporize, denature, separate or otherwiserender inert the hydrocarbon or other contaminate.

It is foreseen that laser radiation at 532 nm, e.g. high frequency 532nm, will be even more effective at exciting and removing hydrocarbonsthan a 1064 nm wavelength, from water based on the known absorptioncharacteristics of water and hydrocarbons.

In various embodiments a combination of more than one wavelength, usedsimultaneously, is foreseen to provide optimal results. When usingmultiple wavelengths, multiple hydrocarbons and contaminants havingdifferent absorption characteristics may be targeted at one time. Forexample wavelengths such as, but not limited to, 1064 nm and 532 nm and355 nm and 266 nm can be used at the same time to achieve optimaldesired results while purifying water.

In various embodiments, one or more wavelengths, for example wavelengthssuch as, but not limited to, 1064 nm and 532 nm and 355 nm and or 266 nmcan be used individually, in sequence when processing the liquid morethan one time, to achieve optimal desired results while purifying orcleaning the liquid.

In various embodiments the same wavelength, e.g. 1064 nm and 532 nm and355 nm and or 266 nm, can be used in sequence when processing the liquidmore than one time to achieve optimal desired results while purifying orcleaning the liquid.

In various embodiments wavelengths of 1064 nm and 532 nm are preferablyselected for targeting hydrocarbons in water, including fresh or saltwater, and the 1064 nm or 532 nm wavelengths may each be utilized alone,and/or together, and/or in sequence in a laser ablation process. 532 nmand 1064 nm are related harmonically as 532 nm is the second harmonic of1064 nm laser light. 1064 divided by 2=532.

In various embodiments, the laser ablation process may be used in amobile device or incorporated into a floating or submerged vessel (e.g.,a motorized vessel) or incorporated into an apparatus that can filterwater around it or process water that passes through it as it floats ormoves. Such a vessel system could be placed inside of a water holdingtank and purify the water or it could be, for example, released into theocean to deal with an oil spill. Instead of the water flowing through astationary system, the system may be mobile and move through the waterand process the water while the vessel moves through the water. Forexample, a self-contained vessel may comprise a laser filter, whereinthe vessel can suck or gather or flow water into it as it moves, orwhile it is stationary, and process the water. In various embodimentsthe self-contained floating or moveable vessel can also be equipped withsensors, e.g., an EX-100 sensor, commercially available athttp://www.advancedsensors.co.uk, that measures parts per million (ppm)of oil or other contaminates present in water. The vessel may beconfigured to activate once a designated level of hydrocarbons orcontaminates is reached. Activation could be automatically set to occurwhen a certain level of hydro-carbon or contaminate is measured.Alternatively, activation could occur, manually or remotely, or viaother suitable means when a hydro-carbons or other contaminates measureat a specified level.

FIG. 5 illustrates an arrangement wherein a laser scanner 40 ispositioned at or near a corner of a vessel 11, for example a cornerjunction of a pipe system or containment vessel 11. As shown, a laserscanner 40 is at corner of pipes or vessel 11, firing parallel to theflow direction. A laser path 15 is illustrated. Such a configurationincludes incorporation of a laser scanning system 40, such as, but notlimited to, those manufactured by G.C. Laser Systems Inc. for the GC-1laser system. Additional scanning systems 40 can also be used in whichthe laser energy of beam 12 exits the system 40 as a cone to trace out aclosed curve of a circle or oval. The laser energy 12 cone can be fireddown the length of the pipe or containment vessel 11 until it terminateson the walls. All water or liquid 20 passing through the pipe 11 mustpass through the laser 12 cone as it flows through the pipe 11. The pipe11 can for example be round or square or rectangle, or other desiredshape.

FIGS. 6-6C illustrate an arrangement wherein a laser scanner 40 ispositioned above a pipe or vessel 11, firing perpendicular to the flowdirection. Such a configuration utilizes a scanning system 40 in whichthe laser beam 12 exits the system 40 as a cone to trace out a closedcurve of a circle or oval. The top view and side views show that asliquid 20 passes past the laser beam 12 circular scan, it is exposed tothe laser beam 12 twice: 1 & 2. The first exposure is as the liquid 20enters the circle, and the second exposure is as the liquid 20 exits thecircle.

The liquid material 20 is processed twice as efficiently in such aconfiguration with a laser beam 12 circular scan as with a linear scanmethod, by comparison, because the liquid 20 gets double the exposure. Alaser beam 12 linear scan, running a line perpendicular to the directionof the flow, in such a configuration allows the material to react withthe laser beam 12 once as the liquid 20 passes.

The side views in FIGS. 6A-6C show different configurations of how thelaser beam 12 cone can be shaped to interact with the material: A:direct shot from scanner into liquid 20 at an angle, e.g., preferably a5 to 45 degree angle (see FIG. 6A). B: Scanner 40 interacts with andoptic 60 such as a telecentric f-theta lens that creates a moreperpendicular tube out of the incoming cone (see FIG. 6B). C: laser 12Cone is fired into a focusing lens 70 such as a regular lens or f-thetalens to create more intense focus in a particular focal plane or zone(see FIG. 6C).

In various embodiments a laser beam can be directed into a chamber at anangle other than 90 degrees.

This type of design can be executed by having a window 90 composed of amaterial which transmits the laser radiation on the pipe or containmentvessel to allow the laser beam to enter the pipe. Fused silica is anexample of such a material for a window. The pipe or containment vessel11 can be square or round or any other desired shape. A square shape, incross section, pipe or container 11 is preferred as allowing a moreefficient exposure of the liquid 20 to a laser beam 12. One face of asquare pipe 11 would preferably feature a fused silica, or othersuitable material, window 90 to allow the laser beam 12 to enter.

FIGS. 7A-7E illustrate examples of some possible laser scanner 40configurations. The laser source or scanner 40 can be designed, forexample, with different optics to create a laser beam 12 having a 2dimensional flat plane (A+C) (see FIGS. 7A-7C), a three dimensional tube(A+D) (see FIGS. 7A and 7D), or a cone scan pattern (B+E) (see FIGS. 7Band 7E). Each scan pattern or path 15 has unique benefits andattributes, for example a scan pattern or path that creates a flat plane(A+C) can produce a laser field wall that is easy to manipulate, while alaser tube (A+D) or cone path (B+E) can allow for two exposures of thematerial that passes through it. Line scanning and/or circular or ovalscanning laser systems 40 can be used.

FIGS. 8A-8D illustrates examples of how one or more laser beams 12 canbe bounced around in a path 15 inside a tube 11 for maximum exposure.The laser light or beam 12 enters a vessel/chamber/tube/pipe 11, whichhas a liquid or fluid therein, or flowing through it, e.g., contaminatedliquid 20, at an angle other than 90 degrees, and can be bounced aroundwith mirrors 80 that are placed either inside thevessel/chamber/tube/pipe 11 (see FIGS. 8C-8D) or on the outside of thevessel/chamber/tube/pipe 11 (see FIG. 8A-8B) behind fused silica (orother appropriate material) windows 90, for example. Having the mirrors80 on the outside of a fused silica window 90 can help keep the mirrorsclean. The laser path 15 can terminate at a target 100, in the liquidover a distance (see FIG. 8D), or on the wall of the tube (see FIG.8A-C). The target 100 can be simply an inert energy dump material or canbe made of a material that will facilitate plasma formation andcavitation bubbles.

As illustrated in FIG. 8A, the mirrors 80 can be spaced apart from oneanother a selected distance on top and bottom portions of avessel/container/tube/pipe 11, wherein the top mirrors 80 are positionedoffset from the bottom mirrors 80. As illustrated in 8B-8D,alternatively a single larger mirror 80 can be placed on interior orexterior top and bottom portions, over the entire length of thevessel/tube/container/pipe 11 for which the laser energy 12 will travelin a path 15. In the examples of FIG. 8A-C a single laser source orscanner 40 is used to provide laser energy 12 that bounces around themirrors within the container in a path 15. In FIG. 8D two lasers 40 areutilized. The two laser scanners 40 may be set to the same or differentwavelengths to target one or more types of hydrocarbons or contaminatespresent in the liquid. If both laser scanners 40 are set to the samewavelength, it will increase the exposure of the liquid to the laserenergy of the particular wavelength. If the laser scanners 40 are set todifferent wavelengths, then more than one type of hydrocarbon orcontaminate may be targeted at the same time. In various embodiments anydesired number of laser scanners 40, e.g., 1 or 2 or 3 or 4 or 5 or 6 ormore as desired may be utilized to maximize exposure of the liquid to aparticular laser wavelength or to target multiple contaminants at onetime.

FIG. 9 is a three dimensional rendering example of a laser path 15 fromFIG. 8. As illustrated, the laser light or energy 12 “wall” or planebounces around in the vessel/container/tube/pipe 11, increasing theamount of exposure the liquid 20 gets to the laser energy 12 as it flowsthrough the vessel/container/tube/pipe 11.

FIG. 10 is a schematic diagram of an embodiment of the process of thepresent invention wherein contaminated liquid 20 flows into a containeror vessel or pipe 11 to undergo a laser ablation process, whereinseparated or transformed hydrocarbons or other contaminants areseparated from the contaminated liquid 20 and flowed to a collectionchamber 16, e.g., continuously flowing therethrough, and wherein cleanor processed water 30 exits the container or pipe or vessel 11 afterbeing exposed to the laser energy. A similar process can be performedwith a submergible vessel. A similar process can also be performedwherein rather than continuously flowing through vessel or pipe 11, thecontaminated water enters a vessel or pipe or chamber 11 and stopsflowing to undergo a laser ablation process. After the laser ablationprocess it can then be flowed to an exit. After the laser ablationprocess contaminants can also be flowed to a collection chamber orseries of chambers. Skimmer devices such as spillover weirs, rotatablepaddles, or flight and rake systems, may be used to assist with removaland flow of separated materials to a collection chamber or collectionssump 16. A collection chamber or series of chambers, perforatedmembranes, or a ventilation system can also be integrated to collect andseparate the gasses that are created in the ablation process.

FIGS. 11-13 show bubbles 18 formed during a laser ablation process. FIG.11 illustrates contaminated liquid 20 that is darker in color than thecontaminated liquid 20 of FIG. 12. Bubbles are starting to form in FIG.11, with more present in FIG. 12 and with the bubbles rising. FIG. 13illustrates a photo that was taken after a red aiming beam was used inthe dark, that shows the path of the laser energy through the liquid.This red aiming beam is replaced by the actual laser beam during theprocess.

In order to confirm repeatability, depending on the parameters and laserpower being used, 1-5 minutes exposure to laser energy such as shown inthe figures, gives noticeable, visible, purifying results.

The following is a list of parts and materials suitable for use in thepresent invention:

PARTS LIST: PART NUMBER DESCRIPTION 10 laser ablation apparatus 11vessel/container/tube/pipe 12 laser energy/light/radiation/beam 13absorption and fluorescence data 15 path 16 collectionchamber/reservoir/sump 18 bubble 20 contaminated water/liquid/fluid 30purified/processed water 40 laser source/laser scanner 60 optic 70focusing lens 80 mirror 90 window 100 target

All measurements disclosed herein are at standard temperature andpressure, at sea level on Earth, unless indicated otherwise. Allmaterials used or intended to be used in a human being arebiocompatible, unless indicated otherwise.

The foregoing embodiments are presented by way of example only; thescope of the present invention is to be limited only by the followingclaims.

The invention claimed is:
 1. A laser ablation and filtration process forremoving one or more contaminates, including hydrocarbons, from a liquidcomprising the following steps: a. housing the liquid in a vessel; andb. cleaning or purifying the liquid by directing laser energy from alaser source through the liquid, wherein the laser energy has at leastone wavelength that denatures, renders inert, breaks down, neutralizes,vaporizes and/or separates the hydrocarbons from the liquid, and whereinthe at least one wavelength is selected from a range of 400 nm to 570nm.
 2. The process of claim 1 further comprising a step of gatheringabsorption, fluorescence and/or microscopy data of the liquid beforedirecting laser energy through the liquid.
 3. The process of claim 2further comprising a step of gathering absorption, fluorescence and/ormicroscopy data of the one or more contaminates in the liquid beforedirecting laser energy through the liquid.
 4. The process of claim 3further comprising a step of tuning the laser source to the at least onewavelength which is a desired wavelength of pulsed, modulated, orcontinuous wave laser energy wherein the laser energy will pass throughthe liquid and will be absorbed by at least the hydrocarbons, andwherein laser energy having a second wavelength is also selected anddirected to the liquid, the second wavelength selected from one of thefollowing ranges: i) 495 nm to 570 nm; or ii) 900 to 1064 nm.
 5. Theprocess of claim 4 further comprising a step of selecting a desiredlaser path for the laser energy to travel within the vessel and throughthe liquid.
 6. The process of claim 1 wherein the laser source includesone or more tuning parameters, and the one or more tuning parameters forthe laser source include wavelength, fluence, pulse duration, modulationrate, pulse profile, beam diameter, pulse frequency, energy, and/orfocal distance.
 7. The process of claim 5 wherein the laser energy isdirected along the laser path for a desired time interval.
 8. Theprocess of claim 1 wherein the contaminated liquid is set to atemperature in a desired pre-set temperature range.
 9. The process ofclaim 1 wherein in step 1 the laser energy is fired directly into theliquid from the source.
 10. The process of claim 1 wherein the laserenergy from the laser source is directed into the contaminated liquidwith assistance of a delivery system such as mirrors, fiber optics,articulated arms, and laser scanners.
 11. The process of claim 1 whereina desired energy density or fluence of the laser energy that is neededto facilitate a reaction can be achieved by firing the laser energydirectly from the laser source.
 12. The process of claim 1 wherein adesired energy density or fluence of the laser energy that is needed tofacilitate a reaction can be achieved by using optics, includingcollimators, mirrors, prisms, custom optics, and/or focusing lenses toachieve desired parameters.
 13. A laser ablation and filtrationapparatus comprising: a vessel for receiving a liquid containingcontaminates, including hydrocarbons; and a laser source tuned fordirecting laser energy through the liquid at a wavelength selected froma range of 495-570 nm for denaturing, rendering inert, neutralizing,vaporizing and/or separating the hydrocarbons from the liquid.
 14. Theapparatus of claim 13 further comprising a collection container forcollecting separated contaminates and by-products.
 15. The apparatus ofclaim 13 wherein the laser source is positioned outside the vessel andfurther comprising a window through which laser energy is directed tothe contaminated liquid.
 16. The apparatus of claim 13 furthercomprising one or more mirrors for directing a path of the laser energythrough the vessel.
 17. The apparatus of claim 16 wherein the mirrorsare on the outside of the vessel.
 18. The apparatus of claim 16 whereinthe mirrors are on the inside of the vessel.
 19. The apparatus of claim14 further comprising one or more optics, including collimators,mirrors, prisms, custom optics, and focusing lenses to achieve desiredparameters.
 20. The apparatus of claim 13 further comprising more thanone laser source.
 21. The apparatus of claim 13 wherein the laser sourceis positioned based on desired parameters to maximize exposure of theliquid to the laser energy, including sizing parameters, angle andinclination of the laser, retention time for a laser process to beapplied and geometry of the containment for proper inclination.
 22. Theapparatus of claim 13 further comprising a series of collectionchambers, perforated membranes, and a ventilation system integrated tocollect and separate gases and other by-products that are created. 23.The apparatus of claim 19 wherein the collection container is physicallyseparated from a path of the laser energy.
 24. The apparatus of claim 19wherein the collection container is optically separated from a path ofthe laser energy.
 25. The apparatus of claim 13 wherein the vessel isconfigured for performing an ablation process outside of a body ofwater.
 26. The apparatus of claim 13 wherein the vessel is submergiblewithin a body of water, an ocean, a lake, or a reservoir.
 27. Theapparatus of claim 13 wherein the vessel is submergible within a cellhousing the contaminated liquid.
 28. The apparatus of claim 26 whereinthe body of water includes the contaminated liquid and the vessel ismobile within the body of water for moving through the contaminatedliquid during an ablation process, while directing laser energy at thecontaminated liquid.
 29. The apparatus of claim 26 wherein the vessel isfloatable for floating within the contaminated liquid during an ablationprocess.
 30. A laser ablation and filtration apparatus comprising: avessel for purifying a fluid containing contaminates, includinghydrocarbons, the vessel including a laser source that is tuned fordirecting laser light energy of at least one wavelength selected from arange of 400 nm to 570 nm through the fluid to be purified fordenaturing, rendering inert, neutralizing, vaporizing and/or separatingthe hydrocarbons from the fluid.
 31. The apparatus of claim 30 whereinthe vessel is submergible within the fluid to be purified.
 32. Theapparatus of claim 31 wherein laser energy is directed outside thevessel to target the hydrocarbons in the fluid.
 33. The apparatus ofclaim 31 wherein fluid is flowed into the vessel and laser energy isdirected within the vessel to target the hydrocarbons in the fluid. 34.The process of claim 1 wherein the at least one wavelength of the laserenergy is selected from a visible light spectrum in the range of 495 to570.
 35. The process of claim 1 wherein the at least one wavelength ofthe laser energy is selected from a visible light spectrum in a range of400 to
 494. 36. The process of claim 1 wherein a second wavelength oflaser energy is selected from a range of 1100 nm to 1220 nm.
 37. Theprocess of claim 1 wherein a second wavelength of the laser energy isselected from a range of 266 nm to 1064 nm.
 38. The process of claim 34wherein the at least one wavelength selected is 532 nm.
 39. The processof claim 38 wherein the laser energy includes more than one wavelengthand wherein the more than one wavelengths that are selected include 532nm and 1064 nm wavelengths.
 40. The apparatus of claim 30 wherein the atleast one wavelength is selected from a range of 495-570 nm.
 41. Theprocess of claim 1 wherein a second wavelength is selected from a rangeof 900-1220 nm.
 42. The apparatus of claim 30 wherein the at least onewavelength is selected from a visible light spectrum in the range of 495to 570, and further including another laser source tunable to a secondwavelength in the range of 900 to 1064 nm.
 43. The apparatus of claim 30wherein the at least one wavelength selected is 532 nm, and furtherincluding another laser source that is tunable to a second wavelength of1064 nm.
 44. The apparatus of claim 13 wherein the apparatus furtherincludes another laser source that is tunable to a second wavelengthselected from the range of 900-1064.